JP2001207044A - Elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an elastomer composition which can be used for automobiles, household electric appliances, toys, miscellaneous goods, or the like, because the composition has an excellent scuffing resistance (a scratching resistance) to the surface of a molding thereof, and is excellent in softening properties, heat resistance, low temperature characteristics, weatherability, strength and moldability, and which can realize high productivity and a low-cost because the composition has the excellent scuffing resistance to the surface, and a coating step can be omitted. SOLUTION: This thermoplastic elastomer composition comprises the following components (a) and (b). Component (a): 100 pts.wt. of a polyester series elastomer. Component (b) comprises the following components (b-1) and (b-2). Component (b-1): 10-60 wt.% of a polypropylene polymer (containing propylene of >=85 wt.%). Component (b-2): a mixture of 40-90 wt.% of an ethylene propylene copolymer rubber (containing propylene of <=75 wt.%), an average dispersion particle diameter of the ethylene propylene series copolymer rubber in the mixture being <=2 &mu;m, flexural modulus of the mixture being 20-700 MPa, Shore D hardness thereof being 20-60, and the content of a polypropylene mixture being 20-900 pts.wt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a molded article having excellent scratch resistance (scratch resistance), flexibility, heat resistance, and the like.
The present invention relates to a thermoplastic elastomer composition that can be used as a material for various molded products having excellent low-temperature characteristics, weather resistance, strength, and moldability.

[0002]

2. Description of the Related Art Thermoplastic elastomers having excellent productivity have been increasingly used for automotive parts, home electric parts, medical parts and miscellaneous goods, for which vulcanized rubber has hitherto been mainly used. Examples thereof include olefin-based elastomers composed of an ethylene-propylene copolymer and polypropylene, polyurethane elastomers, and soft polyvinyl chloride.

However, at present, these molding materials have drawbacks in terms of scratch resistance, flexibility, workability, economy, and recyclability. That is, olefin-based elastomers are relatively inexpensive and have excellent weather resistance and heat resistance, but are inferior in flexibility and scratch resistance. Further, the polyester elastomer has excellent scratch resistance, but has a drawback that it has a large specific gravity and is expensive. Soft vinyl chloride is relatively inexpensive and has excellent weather resistance and scratch resistance, but has the drawback of poor flexibility at low temperatures and poor recyclability.

Some proposals have also been made for elastomer compositions using hydrogenated derivatives of vinyl aromatic compound-conjugated diene compound block copolymers (hereinafter abbreviated as hydrogenated block copolymers). . For example, JP-A-50-14742, JP-A-52-65551,
JP-A-58-206644 discloses compositions in which a hydrogenated block copolymer is blended with a rubber softener and an olefin resin. However, these compositions, like the olefin-based elastomers, also had poor scratch resistance.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned conventional technical problems, and is intended to provide a thermoplastic elastomer having excellent flexibility, weather resistance, heat resistance, low-temperature characteristics, strength, and moldability. An object of the present invention is to provide an elastomer member which is excellent in scratch resistance and does not require surface coating.

[0006]

That is, the present invention provides: (a) a polyester-based elastomer: 100 parts by weight; (b) (b-1) a polypropylene-based polymer (propylene is 85
(B-2) ethylene-propylene-based copolymer rubber (containing 75% by weight or less of propylene): 40-90% by weight. Polypropylene mixture having an average dispersed particle size of polymer rubber of 2 μm or less, a flexural modulus of the mixture of 20 to 700 MPa, a Shore D hardness of 20 to 60, and a melt flow rate of 10 to 60 g / 10 min: 5 to 900 The present invention relates to an elastomer composition comprising parts by weight.

Hereinafter, the present invention will be described in detail. As the polyester elastomer (hereinafter abbreviated as TPEE) as the component (a) of the present invention, the hard segment is a polyester such as polybutylene terephthalate, and the soft segments are polytetramethylene glycol ether (PTMG) and PTMEGT (PTMG and PTMG, respectively). Polyester / polyether type such as polyether such as condensate with terephthalic acid) and polyester / polyester type where hard segment is the same polyester as above and soft segment is aliphatic polyester such as polycaprolactone It is possible. In particular, of these, polyester-polyether type is preferable in order to obtain a softer feeling. Specific examples include "Pelprene" manufactured by Toyobo and "Hytrel" manufactured by Dupont Toray.

In particular, as the TPEE used in the present invention,
(A) the dicarboxylic acid component in which the short-chain dicarboxylic acid component is an aromatic dicarboxylic acid and / or an ester-forming derivative thereof; and (b) the short-chain diol component is an aliphatic diol and / or
Alternatively, the short-chain diol component which is an ester-forming derivative thereof and (c) the long-chain diol component are composed of N represented by the following formula (1) and T represented by the following formula (2), and the ratio of N is 5 to 50 mol. %
The present invention uses a block copolymer obtained by copolymerizing a polyether having an alcoholic hydroxyl group at both ends with a polyether glycol having a number average molecular weight of 400 to 6,000. It is preferable because the low-temperature characteristics, rubber elasticity, flexibility and softness of the elastomer composition are more excellent.

[0009]

Embedded image

[0010]

Embedded image T: —CH ₂ CH ₂ CH ₂ CH ₂ O—
(2)

The component (a) used in the polymerization of the polyetherester block copolymer, that is, the aromatic dicarboxylic acid and its ester-forming derivative include terephthalic acid, isophthalic acid, phthalic acid, and naphthalene-2,6- Examples include dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, 5-sulfoisophthalic acid, and ester-forming derivatives thereof.

Also, alicyclic or aliphatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, succinic acid, oxalic acid, adipic acid, sebacic acid, dodecanediic acid, dimer acid and the like and ester-forming derivatives thereof are used. You may. These may be used alone or in combination of two or more. Preferably, terephthalic acid, isophthalic acid, and naphthalene-2,6-dicarboxylic acid are used.

As the component (b), ie, an aliphatic diol and its ester-forming derivative, a diol having a molecular weight of 300 or less is usually used. Examples include ethylene glycol, 1,3-propylene diol, 1,4-butane diol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, decamethylene glycol, and ester-forming derivatives thereof.

Also, alicyclic diols such as 1,1-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, and ester-forming derivatives thereof; xylylene glycol, bis (p-hydroxy ) Diphenyl, bis (p-hydroxyphenyl) propane, 2,2-bis [4- (2-hydroxyethoxy) phenyl] propane, bis [4 (2-hydroxy) phenyl] sulfone, 1,1-bis [4-
(2-hydroxyethoxy) phenyl] cyclohexane, and the like, and ester-forming derivatives thereof.
Preferably, ethylene glycol, 1,4-butanediol and their ester-forming derivatives are mentioned.

The combination of the above aromatic dicarboxylic acids and / or their ester-forming derivatives with aliphatic diols and / or their ester-forming derivatives results in the hard segment of the polyetherester block copolymer, that is, the short-chain polyester. The preferred combination is a combination of terephthalic acid or terephthalic acid diester and ethylene glycol or 1,4-butanediol (polyethylene terephthalate, polybutylene terephthalate). More preferably, polybutylene terephthalate is preferably used for the hard segment.

The reason for this is that polybutylene terephthalate has a high crystallization rate and is excellent in moldability. Even when a polyetherester block copolymer is used, the balance of physical properties such as rubber elasticity, mechanical properties, heat resistance, and chemical resistance is high. It depends on what is well equipped. Other dicarboxylic acids and their ester-forming derivatives up to 15 mol% in this combination,
Or other diols and their ester-forming derivatives
It can be used by adding up to 5 mol%.

The component (c) of the polyetherester block copolymer, that is, the polyether glycol constituting the long-chain polyester is composed of N and T, and the ratio of N is 5 to 5.
The polyether is 0 mol%, preferably 10 to 20 mol%, and is polyether glycol having alcoholic hydroxyl groups at both ends.

The polyether glycol used in the production of the polyetherester block copolymer is a homo-cation polymerization of 3,3-dimethyloxetane (3,3-DMO), and 3,3-DMO and neopentyl glycol (NP
G), cationic copolymerization of 3,3-DMO with tetrahydrofuran (THF), 3,3-DMO
Terpolymerization of NPG and THF or neopentyl glycol and tetrahydrofuran as raw materials, in the presence of a catalyst showing activity in the presence of an alcoholic hydroxyl group,
It can be produced under reaction conditions under which depolymerization of pure tetramethylene glycol proceeds.

In a copolymer composition in which N in the polyether glycol is less than 5 mol%, if this is a polyetherester block copolymer, satisfactory physical properties may not be obtained particularly at low temperature performance. Not preferred. On the other hand, if the content of N in the polyether glycol exceeds 50 mol%, the glass transition temperature of TPEE increases, and the low-temperature characteristics deteriorate, which is not preferable.

A preferred method for producing a polyether glycol used for producing a polyether ester block copolymer is to prepare a large amount of neopentyl glycol in the presence of a catalyst which is active in the presence of an alcoholic hydroxyl group,
The reaction is carried out at a high temperature at which the depolymerization of pure tetramethylene glycol proceeds and at a low THF concentration, that is, at a high polymer concentration. As catalysts which show activity in the presence of alcoholic hydroxyl groups, heteropolyacids are described in JP-A-60-20366, and salts of heteropolyacids are described in JP-A-61-120830. Can be done. At this time, the requirement that the molar ratio of water or diol to the catalyst is 10 or less is unnecessary under the reaction conditions for providing the polyether glycol of the present invention.

The catalyst exhibiting activity in the presence of an alcoholic hydroxyl group is not particularly limited to heteropolyacid, and benzenesulfonic acid, toluenesulfonic acid and the like may be used. The reason that the copolymerization ratio of neopentyl glycol can be increased in a special reaction condition method that gives a preferable polyether glycol used in the production of the polyetherester block copolymer used in the present invention is that a diol to a catalyst is used. This is because the polymerization can proceed even if the molar ratio of the compound is 30, so that a large amount of neopentyl glycol can be charged. Also, TH
The formation of a polymer molecular chain consisting only of F is suppressed because the polymerization proceeds under the depolymerization conditions of pure poly (tetramethyleneoxy) glycol.

The requirements for the preferred production of the polyether glycol used for the polyetherester block copolymer are summarized as follows. First, there are three requirements. First, a catalyst which is active in the presence of an alcoholic hydroxyl group, for example, a heteropolyacid or a sulfonic acid And secondly, a glycol which prevents propagation of depolymerization as a copolymerized glycol, ie, N
Thirdly, the use of PG is to promote the reaction at a temperature and a polymer concentration at which depolymerization of pure PTMG proceeds in order to make polycondensation at which the copolymerization ratio increases as a main reaction.

In order to advance this polycondensation reaction at a preferable rate, the reaction temperature must be 70 ° C. or higher, preferably 75 ° C. or higher. However, if the reaction temperature is too high, the coloring of the reaction solution or the catalyst becomes strong, which is not preferable. For example, in the case where phosphotungstic acid is used as a catalyst, coloring usually becomes severe above 110 ° C.

Although the catalysts used in the present invention have been mentioned above, preferred catalysts among them include phosphotungstic acid which is commercially available, has good stability at high temperatures and high reaction activity. When a heteropolyacid such as tungstophosphoric acid is used as a catalyst, as the reaction proceeds, the reaction solution is composed of a catalyst layer having a high catalyst concentration and one catalyst.
%, And the reaction is carried out in a two-layer dispersed state. If the stirring is stopped at the end of the reaction and the mixture is allowed to stand, the heavy catalyst layer separates below and the light liquid layer separates above. The upper liquid layer is taken out, and THF, oligomers and dissolved catalyst are removed to obtain a target polymer. A new batch of NPG and THF is supplied to the catalyst layer left below, and a new batch reaction is started. In this way, a polyether ester block copolymer as a raw material of the present invention can be obtained while repeatedly using the catalyst.

When sulfonic acid is used as a catalyst, a catalyst that does not dissolve in the reaction solution, such as Nafion,
Separation of the catalyst is simple and preferred. The amount of NPG to be used is preferably 2 to 10 moles of NPG per 1 equivalent of the catalyst with respect to the amount of the phosphotungstic acid or sulfonic acid used as the catalyst. If the amount of NPG is small, the amount of polymer to be collected at the end of the reaction will be small, and if the amount of NPG is large, the polycondensation reaction will be slow and it will take a long time to increase the degree of polymerization of the polymer.

The water generated by the polycondensation can be taken out and removed as gaseous phase moisture of the reaction system. The composition of the gas phase is mostly THF, and the water content of the gas phase is 0.4 to 2.0 wt.
% Is usually included. Therefore, when removing water, THF is taken out together, and it is necessary to replenish new THF by that much. Since it is necessary to take out the gas phase of the reaction system, the reaction solution is at the boiling temperature. In order to control the boiling temperature, that is, the reaction temperature, to a predetermined value, it is an easy method to control the THF concentration. As a specific operation, TH is adjusted so that the liquid temperature is maintained at a predetermined value.
If the replenishment rate of F was to be controlled, THF extracted together with vapor-phase moisture, a change in composition along with the progress of the reaction and consumption of THF due to polymerization, and a standard operation capable of coping with all these changes could be determined for THF. Will be.

The THF concentration in the reaction solution varies depending on the reaction pressure and the reaction temperature, that is, the boiling pressure and temperature. Therefore, THF
The concentration can be controlled by the reaction pressure given the reaction temperature. The concentration of water in the reaction solution is in dynamic equilibrium with the concentration of water in the gas phase of the reaction system. Therefore, the water concentration in the reaction solution is
It can be controlled by the water concentration in the gas phase of the reaction system.

The number average molecular weight of the polyether glycol used for producing the polyetherester block copolymer is 400 to 6,000, preferably 800 to 3,000.
0, more preferably 1,000 to 2,000. If it is less than 400, the average chain length of the short-chain polyester (hard segment) usually becomes small, depending on the hard / soft segment ratio of the final polyetherester block copolymer to be polymerized, and the melting point drops sharply, resulting in poor heat resistance. Inferior, when used directly as a material as a polyetherester block copolymer,
Alternatively, both are not preferable when the composition is used. Also,
If it exceeds 000, the terminal group concentration in the polyether glycol per unit weight becomes low, and it becomes difficult to polymerize.

The total amount of polyether glycol units (soft segments) in the polyetherester block copolymer is 20 to 90% by weight, preferably 30 to 90% by weight.
７０70% by weight, more preferably 40-60% by weight. In this case, the amount of the polyether glycol unit refers to the weight ratio of the soft segment, not the weight ratio of the charged polyether glycol in all monomers.

In general, the hard segment of the polyetherester block copolymer is a short-chain ester, and the soft segment is composed of a long-chain ester. It is connected to a segment. A unit including a unit constituting an ester bond at one end of the polyether portion was defined as a soft segment for convenience.

The ratio of this hard / soft segment is ¹
It can be accurately quantified by H-NMR. If the amount of the soft segment is less than 20% by weight, the softness is inferior, and the soft feeling of the steering wheel of the present invention is particularly unfavorably deteriorated. In addition, this amount is 90% by weight.
If it exceeds, it will be too soft, and it will be inferior in followability with the metal core, which is not preferable.

The polyetherester block copolymer can be produced by a known method. For example, a lower alcohol diester of a dicarboxylic acid, a transesterification reaction of an excessive amount of a low molecular weight glycol and a polyether glycol in the presence of a catalyst, followed by polycondensation of the resulting reaction product under reduced pressure, or a dicarboxylic acid and a glycol and A method in which polyether glycol is subjected to an esterification reaction in the presence of a catalyst, and then the resulting product is subjected to polycondensation. Alternatively, a short-chain polyester (for example, polybutylene terephthalate) is prepared in advance, and then another dicarboxylic acid, diol or Any method such as a method of adding ether glycol or adding another copolymerized polyester and performing randomization by transesterification may be employed.

As a catalyst common to the transesterification reaction or esterification reaction and the polycondensation reaction used for producing the polyetherester block copolymer, tetra (isopropoxy) titanate and tetra (n-butoxy) titanate are used. Representative tetraalkyl titanates, reaction products of these tetraalkyl titanates with alkylene glycols, partial hydrolysates of tetraalkyl titanates, metal salts of titanium hexaalkoxides, titanium carboxylate salts, titanium-based compounds such as titanyl compounds Catalysts are preferred. Also, mono-n-butyl monohydroxytin oxide, mono-n-butyltin triacetate, mono-n
Monoalkyltin compounds such as -butyltin monooctylate and mono-n-butyltin monoacetate, dialkyls such as di-n-butyltin oxide, di-n-butyltin diacetate, diphenyltin oxide, diphenyltin diacetate and di-n-butyltin dioctylate Alternatively, a diaryl) tin compound can be used.

In addition, catalysts such as metals such as Mg, Pb, Zr and Zn, metal oxides and metal salt catalysts are useful. These catalysts may be used alone or in combination of two or more.

The amount of the esterification or polycondensation catalyst to be added is preferably 0.005 to 0.5% by weight, particularly preferably 0.03 to 0.2% by weight, based on the produced polymer. These catalysts may be added at the beginning of the transesterification or esterification reaction and may or may not be added again during the polycondensation reaction.

Further, a polycarboxylic acid, a polyfunctional hydroxy compound, an oxyacid, or the like may be copolymerized as a part of the dicarboxylic acid or the glycol. The polyfunctional component effectively acts as a high viscosity component, and its copolymerizable range is 3 mol% or less. Those that can be used as such a polyfunctional component include trimellitic acid, trimesic acid, pyromellitic acid, benzophenonetetracarboxylic acid, butanetetracarboxylic acid, glycerin, pentaerythritol and their esters, acid anhydrides, and the like. Can be.

Further, if necessary, the polyether glycol may be partially substituted with another polyether glycol. Examples of the polyether glycol used for such substitution include poly (ethyleneoxy) glycol,
Poly (propyleneoxy) glycol, poly (tetramethyleneoxy) glycol, poly (1,2-propyleneoxy) glycol, a block or random copolymer of ethylene oxide and propylene oxide, THF and 3-
Examples include a random copolymer of methyl THF, a block or random copolymer of ethylene oxide and THF, poly (2-methyl-1,3-propyleneoxy) glycol, poly (propyleneoxy) diimidodiacid, and the like.

The number average molecular weight of the polyether glycol used for these substitutions is preferably from 400 to 6,000, more preferably from 1,000 to 3,000. Preferred substituted polyether glycols include poly (tetramethyleneoxy) glycol. When poly (tetramethyleneoxy) glycol is used for substitution, if the number average molecular weight (Mn) exceeds 1,800, the molecular weight distribution [Mv / Mn: Mn is the number average molecular weight determined from the terminal hydroxyl value, Mv is the formula Mv = Anti log (0.493 l
og η + 3.0646). However, η is the melt viscosity at a temperature of 40 ° C. expressed in poise.] Depending on the case, crystallization may occur to give an undesirable result in low-temperature performance.

The value of the molecular weight distribution (Mv / Mn) is 1.
It is more preferable to use a material as narrow as 6 or less. More preferably, it is 1.5 or less. Preferably, however, the substituted polyether glycol is used in a range of not more than 90% by weight of the polyether glycol used in the present invention. If this value exceeds 90% by weight, depending on the content of the neopentyl oxide unit in the polyether glycol used in the present invention, in general, satisfactory results in physical properties such as water resistance and low temperature performance cannot be obtained. Therefore, selection according to the application is necessary.

The degree of polymerization of the polyetherester block copolymer thus polymerized is generally determined by the relative solution viscosity (η
rel), intrinsic viscosity ([η]), and melt flow rate (MFR). In the present invention, the melt flow rate (230 ° C., 2.16 kg weight, hereinafter referred to as MFR)
Abbreviation).

The MFR is 0.5 to 100 g / 10 min, preferably 5 to 50 g / 10 min, and more preferably 10 to 3 g.
0 g / 10 minutes. If the MFR is less than 0.5 g / 10 minutes, the injection moldability is poor and short shots are caused, which is not preferable. On the other hand, if the MFR exceeds 100 g / 10 minutes, the mechanical properties (e.g., breaking strength, elongation at break), abrasion, compression set (C-Set) and the like are inferior. The Shore D hardness of the polyetherester block copolymer of the present invention may be in the range of 20 to 70, more preferably 25 to 50, and the soft segment amount is appropriately selected. If the Shore D hardness is less than 20, the strength and heat resistance of the obtained thermoplastic elastomer composition will be insufficient, which is not preferable. Also, Shore D is 7
If it exceeds 0, the resulting thermoplastic elastomer will be insufficient in flexibility and softness, which is not preferable.

The polypropylene mixture as the component (b) of the present invention is, for example, a propylene copolymer mixture obtained by at least two or more sequential polymerizations. In the first step, a propylene homopolymer or propylene and α-
An olefin copolymer (containing 85% by weight or more of propylene) or an ethylene-propylene copolymer (containing 85% by weight or more of propylene) is formed by polymerization to obtain a component (b-
1), and ethylene-propylene (containing 75% by weight or less of propylene) or ethylene-propylene-α-olefin (which may contain a small amount of diene) copolymer (75% by weight or less of propylene) Is formed by polymerization to produce component (b-2).

In the polymerization of propylene in the first step, the obtained polypropylene has an isotactic index of 80% or more,
Preferably an amount of at least 85%, more preferably at least 90%, of ethylene or α-olefin, such as butene-1, pentene-1,4-methyl-pentene-
1, hexene-1 and octene-1 or a combination thereof.

The monomers used for polymerizing the ethylene-propylene copolymer or ethylene-propylene-α-olefin copolymer after the second step are propylene and ethylene and / or α-olefin (for example, butene-
1, pentene-1, 4-methyl-pentene-1, hexene-1, and octene-1 or a combination thereof). The polymerization of the copolymer after the second step is carried out by conjugated or non-conjugated dienes, for example, butadiene, 1,4-
It can be carried out in the presence of hexadiene, 1,5-hexadiene, and ethylene-norbornene-1. The diene, when present, is typically from 0.5 to 10% by weight, based on the weight of all monomers used in the second and subsequent steps.

The amount of (b-1) in the polypropylene composition of component (b) is 10 to 60% by weight, preferably 15 to 60% by weight.
50% by weight, the amount of (b-2) is 40 to 90% by weight, preferably 50 to 85% by weight.

The total amount of ethylene copolymerized in the polypropylene mixture of the component (b) is 15 to 60% by weight, preferably 17 to 45% by weight, more preferably 20 to 3% by weight.
5% by weight. Further, the amount of all α-olefins copolymerized in the polypropylene mixture of (b) is 0 to 30% by weight, preferably 3 to 20% by weight, more preferably 5 to 5% by weight.
10% by weight.

The mixture (b) was subjected to differential scanning calorimetry (D
SC) shows at least one melting peak present at a temperature above 120 ° C., preferably above 140 ° C. Further, the mixture (b) has a flexural modulus of 20 to 700 MPa, preferably 50 to 300 MPa.
MPa, more preferably 70 to 200 MPa. The mixture (b) has a Shore D hardness of 20 to 60,
Preferably it is 30-50.

The melt flow rate of the mixture (b) (measured according to ASTM D1238, 230 ° C., 2.16 kg load; hereinafter abbreviated as MFR) is 10 to 10.
60 g / 10 min, preferably 12 to 50 g / 10 min, more preferably 15 to 40 g / 10 min. If the MFR is less than 10 g / 10 minutes, the melt viscosity of the elastomer composition is high, and the moldability (flowability) of the elastomer composition is lowered, and the appearance of a molded product is deteriorated (the generation of flow marks). Further, the MFR is 10 g / 10
If the amount is less than minutes, the scratch resistance of the elastomer composition also decreases, which is not preferable. On the other hand, the MFR is 60 g / 10
If the amount exceeds minutes, the strength and heat resistance of the elastomer composition are undesirably reduced.

The average particle size of the ethylene-propylene copolymer rubber dispersed in the mixture (b) is 2 μm or less.
Preferably it is 1.5 μm or less. If the average dispersed particle size of the rubber exceeds 2 μm, the scratch resistance of the elastomer composition is extremely lowered, which is not preferable.

The catalyst used for the polymerization of the polypropylene mixture of component (b) is a Ziegler-Natta type catalyst.
Preferred catalysts are reaction products of a solid catalyst component containing a titanium compound and an electron donor compound (internal donor) supported on magnesium chloride with a trialkylaluminum compound and an electron donor compound (external donor). . As the method for preparing the catalyst and the method for polymerizing the component (b),
For example, JP-A-3-205439 and JP-A-6-2
No. 5367, JP-A-6-25489 and the like.

The blending amount of the polypropylene mixture of the component (b) in the thermoplastic elastomer composition of the present invention is TPE
5 to 900 parts by weight per 100 parts by weight of component E (a)
Preferably 10 to 500 parts by weight, more preferably 15 parts by weight.
２００200 parts by weight. If the amount of the polypropylene mixture of the component (b) exceeds 900 parts by weight, the rubber elasticity decreases and the low-temperature characteristics deteriorate, which is not preferable. Also,
If the blending amount of the polypropylene mixture of the component (b) is less than 5 parts by weight, the appearance of the molded thermoplastic elastomer composition is deteriorated (flow marks are generated), and the specific gravity is undesirably high.

As the polypropylene mixture of the component (b) used in the present invention, Adflex, Hifax
(Manufactured by Montell, Catalloy TPO series) or the like.

Further, the elastomer composition of the present invention includes:
If necessary, a polyolefin resin (component c) can be added. Specific examples of polyolefin resins that can be added include polyethylene resins and polypropylene resins. Examples of the polyethylene resin include low-density polyethylene, linear low-density polyethylene, high-density polyethylene, and a copolymer of ethylene and an α-olefin having 3 to 8 carbon atoms.

In the case of a copolymer of ethylene and an α-olefin having 3 to 8 carbon atoms, the α-olefin in the copolymer may be propylene, butene-1, isobutene, pentene-
1, hexene-1, 4-methylpentene-1, octene-1 and the like. The ratio of α-olefin is 3
What is 0% by weight or less is used.

The polypropylene resin is a propylene homopolymer or a copolymer of propylene and an α-olefin having 2 to 8 carbon atoms (hereinafter abbreviated as propylene resin). In the case of a copolymer of propylene and an α-olefin having 2 to 8 carbon atoms, the α-olefin in the copolymer may be ethylene, butene-1, isobutene, pentene-
1, hexene-1, 4-methylpentene-1, octene-1 and the like. The ratio of α-olefin is 3
What is 0% by weight or less is used. These propylene-based resins can be synthesized by a conventionally known method, for example, a propylene homopolymer synthesized using a Ziegler-Natta type catalyst, or a copolymer of random or block propylene and an α-olefin. Is raised.

Further, the composition of the present invention may optionally contain a plasticizer. Examples of such a plasticizer include phthalic acid esters such as dioctyl phthalate, dibutyl phthalate, diethyl phthalate, butyl benzyl phthalate, di-2-ethylhexyl phthalate, diisodecyl phthalate, diundecyl phthalate, diisononyl phthalate: tricresyl phosphate, triethyl phosphate, Tributyl phosphate, tri-2-ethylhexyl phosphate, trimethylhexyl phosphate, tris-chloroethyl phosphate, tris-
Phosphates such as dichloropropyl phosphate: octyl trimellitate, isodecyl trimellitate, trimellitate, dipentaerythritol esters, dioctyl adipate, dimethyl adipate, di-2-ethylhexyl azelate,
Dioctyl azelate, dioctyl sebacate, di-2
Fatty acid esters such as ethylhexyl sebacate and methylacetyl ricinocate: pyromellitic esters such as octyl pyromellitic acid: epoxy plasticizers such as epoxidized soybean oil, epoxidized linseed oil, and epoxidized fatty acid alkyl esters: Polyether plasticizers such as adipic acid ether ester and polyether: liquid N
Liquid rubbers such as BR, liquid acrylic rubber and liquid polybutadiene: non-aromatic paraffin oils and the like.

These plasticizers can be used alone or in combination of two or more. The addition amount of the plasticizer is appropriately selected according to the required hardness and physical properties, but is preferably 0 to 50 parts by weight per 100 parts by weight of the composition.

Further, the present elastomer composition contains an inorganic filler, a stabilizer, a lubricant, a coloring agent, a silicone oil, a foaming agent,
A flame retardant or the like may be added. Examples of the inorganic filler include calcium carbonate, talc, magnesium hydroxide, mica, barium sulfate, silicic acid (white carbon), titanium oxide, and carbon black. Examples of the stabilizer include a hindered phenol-based antioxidant, a phosphorus-based heat stabilizer, a hindered amine-based light stabilizer, and a benzotriazole-based UV absorber. Examples of the lubricant include stearic acid, stearic acid esters, and metal salts of stearic acid.

In general, any method known in the art for blending polymer components may be used to prepare the elastomeric composition of the present invention.
In order to obtain the most homogeneous blend, a method of melt-kneading using various kinds of kneading machines such as commonly used mixing rolls, kneaders, Banbury mixers and extruders is desirable. Before melt-kneading, these compounds are dry-blended in advance using a mixer such as a Henschel mixer, tumbler or ribbon blender, and the mixture is melt-kneaded to obtain a homogeneous elastomer composition.

As the molding method of the elastomer composition of the present invention, injection molding, extrusion molding, compression molding and the like can be applied, but it has a feature that it is particularly excellent in moldability at the time of injection molding. When performing injection molding, a normal plastic molding machine can be used, and an injection molded product can be obtained in a short time. In addition, the elastomer composition has an advantage that the sprue portion and the runner portion can be recycled because of its excellent thermal stability.

[0061]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the examples and comparative examples, the test methods used for various evaluation methods are as follows. (1) Shore D hardness [-]: ASTM D2240, D
Type, measured at 23 ° C.

(2) Melt flow rate (MFR) [g
/ 10 min]: ASTM D1238, 230 ° C, 2.1
It was measured under a load of 6 kg.

(3) Tensile strength [kgf / cm ² ]: JI
SK6251, No. 3 dumbbell, and a sample used a 2 mm-thick press sheet.

(4) Elongation [%]: JIS K6251,
A No. 3 dumbbell and a sample used a 2 mm-thick press sheet.

(5) Rebound resilience [%]: JIS K625
5. Lupke pendulum, 23 ° C

(6) Embrittlement temperature [° C.]: JIS K626
1. Gehman torsion test, t100 temperature

(7) Scratch resistance and gloss retention [%]: A flat plate having a smooth surface was formed by injection molding. A flat plate is placed horizontally, and a cotton cloth to which a load of 40 g / cm ² is applied is placed.
Reciprocated twice. The glossiness of the friction surface is determined according to JIS K7105.
(E1), and the retention ratio from the glossiness (E0) before friction; (E1 / E0) × 100 (%) was determined.

(8) Crack drop test: A flat plate having a surface grain (matte, edging depth of about 20 microns) was formed by injection molding. The plate was left in an oven at 100 ° C. for 168 hours. After being taken out of the oven, the surface condition was visually observed, and those having no change were evaluated as ○, slightly glossy as Δ, and glossy as ×.

(9) Formability: A flat plate having a length of 150 mm, a width of 100 mm and a thickness of 2 mm was molded by an injection molding machine under the following conditions. The appearance of the molded product was visually observed such as flow mark and gloss, and a good one was evaluated as ○, a slightly poor one as Δ, and a poor one as ×. Cylinder temperature C
1: 200 ° C., C2: 210 ° C., C3: 210 ° C., nozzle temperature: 200 ° C., injection speed: low speed, mold temperature: 40 ° C. The components used in Examples and Comparative Examples are as follows. is there.

Component (a): As the polyoxyalkylene glycol used for the soft segment of the polyetherester block copolymer, the following was used. (1) Neopentyl glycol copolymer poly (tetramethyleneoxy) glycol (copolymer of T and N, both ends of which are alcoholic hydroxyl groups): Asahi Kasei Corporation
Mn = 1480, Mv / Mn = 1.73, N content =
12 mol%

Component (a) -1 (TPEE component-1): 1
5-liter Mitsubishi Heavy Industries Conical Reactor (V
CR), dimethyl terephthalate (Mitsubishi Kasei Corporation)
1520 g (manufactured by Wako Pure Chemical Industries, Ltd., reagent grade, hereinafter the same) 1060 g
g, the polyoxyalkylene glycol of the above (1) is 3
200 g and 15 g of Irganox 1010 (manufactured by Ciba Geigy) were charged, and after nitrogen replacement, 20 g in a nitrogen atmosphere.
The temperature was raised to 0 ° C. Then, 1.5 g of tetraisopropoxytitanate (Reagent 1st grade, manufactured by Tokyo Chemical Industry, same hereafter) was added. Then, after holding at 200 ° C. for 30 minutes, 230
C., and the ester exchange reaction was carried out for 2 hours while stirring at a rotation speed of 150 rpm. The amount of methanol distilled out was 94% of the theoretical amount. Then raise the temperature to 25
0 ° C., the pressure was reduced to 0.5 mmHg over 30 minutes while stirring at a rotation speed of 50 rpm, and then over about 3 hours,
The condensation reaction was carried out until no increase in torque occurred.

When the contents of the reactor were extracted from the lower part, a polyetherester block copolymer was obtained as a transparent viscous polymer. This was pelletized by strand cutting and vacuum dried at 70 ° C. for 12 hours. The carbon black master pellet (Royal Black RB90
05), 1 part by weight of Irganox 1010, 0.15 part by weight of dilauryl thiopropionate (DLTP, manufactured by Yoshitomi Pharmaceutical Co., Ltd.), and TINUVIN
327 (manufactured by Ciba Geigy) in 0.1 parts by weight
A thermoplastic elastomer composition was obtained by melt-blending at 30 ° C. with an extruder. The Shore D hardness of this thermoplastic elastomer composition was 32, and the MFR was 23 g / 10 minutes.

Component (a) -2 (TPEE component-2): T
Dimethyl terephthalate 20 charged in the synthesis of PEE-1
70 g, 1,440 g of 1,4-butanediol, 2750 g of the polyoxyalkylene glycol of the above (1)
A transesterification reaction and a condensation reaction were carried out in the same manner except for charging. The kind of the additive and the mixing ratio were similarly measured. The obtained thermoplastic elastomer composition had a Shore D hardness of 40 and an MFR of 21 g / 10 min.

Component (a) -3 (TPEE component-3): T
A transesterification reaction and a condensation reaction were carried out in the same manner as in the synthesis of PEE-1 except that the amount of the polyoxyalkylene glycol used in the above (1) was changed to 2500 g. The kind of the additive and the mixing ratio were similarly measured. The resulting thermoplastic elastomer composition had a Shore D hardness of 45 and an MFR of 20 g / 10
Minutes.

Component (a) -4 (TPEE component-4): T
Dimethyl terephthalate 24 charged in the synthesis of PEE-1
90 g, 1,730 g of 1,4-butanediol, 2050 g of the polyoxyalkylene glycol of the above (1)
A transesterification reaction and a condensation reaction were carried out in the same manner as above. The kind of the additive and the mixing ratio were similarly measured. The resulting thermoplastic elastomer composition had a Shore D hardness of 5
6, MFR was 21 g / 10 minutes.

Component (a) -5 (TPEE component-5): manufactured by Toyobo Co., Ltd., Perprene P40H (polyetherester TPEE, Shore D hardness; 37, MFR; 23.
0)

Component (a) -6 (TPEE component-6): manufactured by Toyobo Co., Ltd., Perprene S2002 (polyester T
PEE, Shore D hardness; 53, MFR; 12 g / 10
Minutes)

Component (b): Preparation of solid catalyst; MgCl ₂
Was completely dissolved, 49.5 g of anhydrous MgCl ₂ and 49.5 g of absolute ethanol, 100 ml of petrolatum oil and 100 ml of silicone oil were stirred at 120 ° C. in a nitrogen atmosphere. The mixture was then filled with 1500 ml of pre-filled 150 ml of petrolatum oil and 150 ml of silicone oil.
after transfer to an autoclave at 120 ° C., 3000
The mixture was stirred at rpm for 3 minutes. The mixture is cooled n
-Added under stirring in 1000 ml of heptane,
spherical solid l ₂ · 3EtOH was precipitated (average particle size 3
0-150 μm). Further, the obtained solid was dried under a nitrogen atmosphere while increasing the temperature from 50 ° C. to 100 ° C.
The H / MgCl ₂ molar ratio was adjusted to 1.27. The obtained solid had a porosity of 0.139 cc / g and a surface area of 9.1 m ² / g.
g, bulk density 0.564 g / cc.

25 g of this solid (carrier) was mixed with TiCl ₄ 6
25 cc in an autoclave with stirring and containing
C. under a nitrogen atmosphere. Further, the temperature of the autoclave was raised to 100 ° C. over 1 hour. When the temperature reached 40 ° C. in the heating process, diisobutyl phthalate was added at a molar ratio of 1/8 of magnesium. 100 ℃
After stirring for 2 hours, the mixture was allowed to stand at the same temperature to precipitate a solid.
The supernatant was removed by suction with a siphon. TiCl ₄ 5
50 ml was newly added, and the mixture was stirred at 120 ° C. for 1 hour and allowed to stand. After the supernatant was removed by suction with a siphon, the remaining solid was washed with 200 ml of anhydrous hexane six times at 60 ° C. and three times at room temperature. After drying in vacuum, it was used as a polymerization catalyst for component (b).

The components (b) -1 and (b) -2 were polymerized by the following method. The polymerization was carried out continuously in a series of reactors equipped with a device for transferring sequentially from one reactor to the next. In a 22 liter stirred autoclave, consist of 16 liters of liquid propylene at 20 ° C. and a mixture of about 0.15 g of the above-mentioned solid catalyst, 75 ml of a 10% hexane solution of triethylaluminum and cyclohexylmethyldimethoxysilane (CMMS). A polymerization catalyst (Al / CMMS molar ratio 7.5) was added,
For 24 minutes. The prepolymer was then sent to a first reactor in the gas phase where propylene homopolymerization was performed. Further, the polymer was transferred to a second reactor, where copolymerization of ethylene and propylene was performed. Table 1 shows the polymerization conditions of the first and second reactors and the properties of the final product obtained.

[0081]

[Table 1]

Component (b) -3: Cataloy Adflex KS-084P, manufactured by Montell, MFR 30 g / 10
Minutes. Flexural modulus 108 MPa, Shore D hardness 44, average dispersed particle size of rubber 0.4 μm.

Component (b) -4: Cataloy Adflex KS-359P, MFR 12 g / 10, manufactured by Montell
Minutes. Flexural modulus 83 MPa, Shore D hardness 41, average dispersed particle size of rubber 0.6 μm.

Component (b) -5: Cataloy Adflex KS-221P, MFR 2.5 g / 1, manufactured by Montell
0 minutes. Flexural modulus 350 MPa, Shore D hardness 53, average dispersed particle size of rubber 0.5 μm.

Component (c) -1 Showaromer MK711 (block type polypropylene) manufactured by JPO, MFR 30 g / 10 min. Flexural modulus 1400MPa

Examples 1 to 8 TPEEs (a) -1, (a) -2, (a) -3,
Using (a) -4, (a) -5, and (a) -6, and using (b) -1 as a polypropylene mixture, blending with a Henschel mixer at each ratio shown in Tables 1 and 2,
The mixture was melt-kneaded at 220 ° C. with a 45 mm diameter co-rotating twin screw extruder to obtain pellets of the elastomer composition. Tables 2 and 3 show the results of physical properties and molding processability.

[0087]

[Table 2]

[0088]

[Table 3]

Examples 9 to 12 (a) -2 was used as TPEE, and (b) -2, (b) -3, (b) -4, and (b) were used as polypropylene mixtures.
-5, and blended in a Henschel mixer at the respective ratios shown in Table 4, and then melt-kneaded at 220 ° C. with a 45 mm diameter co-directional twin screw extruder to obtain elastomer composition pellets. Table 4 shows the results of the physical properties and the molding processability.

[0090]

[Table 4]

Examples 13 and 14 (a) -2 was used as TPEE, (b) -1 was used as a polypropylene mixture, and (c) -1 was used as a polyolefin resin. After blending with a Henschel mixer, the mixture was melt-kneaded with a 45 mm diameter co-directional twin-screw extruder at 220 ° C to obtain pellets of an elastomer composition. Table 5 shows the results of the physical properties and the molding processability.

[0092]

[Table 5]

Comparative Examples 1 to 3 (a) -2 was used as TPEE, (b) -1 was used as a polypropylene mixture, and Sa, which is an extruded blend type TPO (PP / EPDM blend), was used as a comparison.
ntoprene 203-40 (flexural modulus 80MP)
a, Shore D hardness of 40, MFR of 8 g / 10 min, rubber dispersion particle size of 9 μm), and kneading at the respective ratios shown in Table 6 in the same manner as in Examples 1-4 to evaluate. The results are shown in Table 6. From this result, it is clear that the composition outside the range of the present invention has any bad physical properties.

[0094]

[Table 6]

[0095]

The elastomer composition obtained by the present invention is excellent in scratch resistance, strength, heat resistance, flexibility, and moldability, so that it can be suitably used in the fields of automobile parts, home electric parts, toys, miscellaneous goods and the like. Suitable for car interior parts such as instrument panels, armrests, steering wheels (steering wheels), horn pads, etc., and car interior and exterior parts such as wind moldings and bumpers that require a product appearance due to their excellent scratch resistance. Can be used for
Further, since the surface of the molded article is excellent in scratch resistance and molding workability, the coating step which has been conventionally required can be eliminated, so that high productivity and low cost can be realized.

Continued on front page F-term (reference) 4J002 BB12X BB14X BB15X BB15Y CF03W CF10W CF18W FA08Y FD010 FD020 FD030 FD170 4J029 AA03 AB01 AC03 AE01 BA02 BA03 BA04 BA05 BD03A BD10 BF25 CA02 CB04 J02 CB05 CB06 JCB CB05 CDB

Claims (4)

[Claims] 1. A thermoplastic elastomer composition comprising the following components (a) and (b): (A) polyester-based elastomer: 100 parts by weight (b) (b-1) polypropylene-based polymer (propylene is 85
(B-2) ethylene-propylene-based copolymer rubber (containing 75% by weight or less of propylene): 40 to 90% by weight, wherein ethylene in the mixture is 40 to 90% by weight. The average dispersion particle size of the propylene copolymer rubber is 2 μm or less, the flexural modulus of the mixture is 20 to 700 MPa, and the Shore D hardness is 20 to
60, a polypropylene mixture: 5 to 900 parts by weight of an elastomer composition. 2. The polyester-based elastomer is a polyetherester block copolymer having a Shore D hardness of 20 to 70 obtained by copolymerizing the following components (a), (b) and (c). The elastomer composition according to claim 1, wherein (A) a dicarboxylic acid component in which the short-chain dicarboxylic acid component is an aromatic dicarboxylic acid and / or an ester-forming derivative thereof; and (b) a short-chain diol in which the short-chain diol component is an aliphatic diol and / or an ester-forming derivative thereof. Component (c) The long-chain diol component comprises a neopentylene oxide structural unit (hereinafter abbreviated as N) represented by the following formula (1) and a tetramethylene oxide structural unit (hereinafter abbreviated as T) represented by the following formula (2)
A polyether having an N ratio of 5 to 50 mol%, an alcoholic hydroxyl group at both terminals, and a number average molecular weight of 400 to 6,000. Embedded image T: —CH ₂ CH ₂ CH ₂ CH ₂ O— (2) 3. The polypropylene composition (b) having a melt flow rate of 10 to 60 g / 10 minutes.
The elastomer composition as described in the above. 4. The polypropylene composition (b) is a mixture mainly composed of polypropylene obtained by sequential polymerization of at least two or more stages. In the first step, a homopolymer of propylene or a mixture of propylene and an α-olefin is used. After forming a copolymer (containing 85% by weight or more of propylene) or an ethylene-propylene copolymer (containing 85% by weight or more of propylene) by polymerization, ethylene-propylene containing a small amount of a diene as required in the second and subsequent steps 3. The elastomer composition according to claim 1, wherein the ethylene-propylene-α-olefin copolymer is formed by polymerization.